Manufacture of new azo dyestuffs



Patented May 19, 1942 r i i r UNITED STATES PATENT OFFICE.

MANUFACTURE or NEW AZO DYESTUFFS Wilfrid Herbert Cliffe, Blackley, Manchester,

England, assignor to Imperial Chemical Industries Limited, a, corporation of Great Britain No Drawing. Original application July "13, 1938',

Serial No. 219,097.

Divided and this application April 18', 1940; Serial No. 330,427. In Great Britain July 14, 1937 6 Claims.

This invention relates to new disaz o dyestuffs and to their manufacture.

An object of the invention is to provide new Y disazo dyestufis.

A further object is to provide-- terized by very good fastness to washing, milling and light. i

The invention will be understood by a consideration of the following examples '(which are new disazo dyestuffs wh1ch are soluble in w'a purely illustrative and not limiting), in which ter. A further object'is to provide new acid the parts are parts by Weight. disazo dyestuffs suitable for W001 and silk; A further object is to provide a process for they Example 1 manufacture of such new disazo dyestuffs. Other objects will appear hereinafter. 33.1 parts of 3:3-d1ammo-6 -methylbenzoyl- 4 T d t fi of the ihventionare watepsob N-benzylan1lide are dissolved in a mixture of uble disaz o dyestuffs andare obtained either by Parts of 36% aqueous hydroFhlonc i coupling tetrazotized diaminobenzoyl-N-benzyl 9 Parts water and tetrazotlzefl, at 91 anilides, as defined below, with two molecular with a solution of 17.2 parts of sodmm n1tr1te m proportions of the same or different coupling 125 parts of watertetmzo solutipn is m components, by coupling a diazofized added gradually to an ce-cold solution containpound corresponding, to the diamino-ben'zoyl-N- mg 81 P l D the 111In salt of l-acetyl-amibenzylanilides above mentioned, but having a f 9 Td qa part5 nitro substituent in place of either but notboth of anhydrous 'Y m 600 Parts of amino substituents, with one molecularproporwatercouphng 15 rapid P the dyestufi is tion of a couplng component, reducing the'nitro Salted outgfiltered Off and dned; The new substituent to an amino substituent, diazotizing stufilhasi n the m of t m the formulm and thencoupling with one molecular proportion V l r of the same or a different coupling component. H 7 L 6 l Thediamino benzoylN-benzyl anilides referred 2 HaC-C-N on o on "N-o-om to above are those of the formula: 01!

.. N=N .c- N= Hols s0=H i m Qmsoan I 30 H.038

It is soluble in water. It dyes wool from an acid F or neutral bath in bright bluish-red shades. The

' dyeings'have very good fastness to washing, milling and light.

The 3 3'-diamino-6' -methylbenzoyl N-benzyl- I V anilide, which is used above and is a new comu pound, is made as follows: in Whlch X and X are hydrogen or methyl- :1 I A solution containing 60.5 parts of 2-benzyls c pli p n n s I e alphanaphtholsulamino-4-nitr0--to1uene and 46.4 parts of m-nitro- 1110 a ids, Substituted aminonaphthfllsulfomc benzoyl chloride in 200 parts of toluene is boiled d a d y y a o o u fo c acidsuntil interactionis complete. The 3:3'-dinitro- The new dyestuffs must contain a sufliciency f t 1 1- 1 1 172.. Of Sulfonic acid ps o ensure that they are 1'73?) which remains is reduced to the required soluble in water. These sulfonic groups need to mi M 3 12 by means of i and 11ybe i in y present in o r e f the drochloric acidin either Water or ethyl alcohol. stuif components. i V

The diaminoor nitroaminobenzoyl-"N-benzyl- Example 2 anilides may be obtained by condensing a mono- Y nitro-N-benzylarylamine of the benzene series A tetrazo solution obtained as in Example l is with a nitroaroyl chloride of the benzene'series, added to a solution containing 61 parts of the and then reducing one or both nitro substituents. sodium salt of 2-acetylamino-8-naphthol-6-sul- The new dyestuffs dye wool from a. neutral or fonic' acid and 40 parts of anhydrous sodium acid bath and the resulting dyeings are ehalae-v carbonate in 800 parts of water. Coupling is 1 rapid and the dyestufi' is filtered off and dried. The dyestufl has, in the form of free acid, the formula:

II I HaC-C-N N=N' It is soluble in water. It dyesw'ool from an acid or neutral bath in bright scdrlet'sh'ades. .The

dyeings have very good fastness to washing, millcomplete. I The resulting 4:3-dinitro-benzoyl-N- benzylanilide (M. P. 147 C.) is then reduced to the required diamine (M. P. 179 C.) by means of ironand hydrochloric acid in either water or ethylalcohol.

Further dyestuffs obtained according to the ing, and light. invention are given in the following table:

g Diazo component Coupling component Shade on wool 4 lmol. of 3:3-diamino-6-mcthylbenzoyl-N-benzylaflilid'e; 2 mols.lof 1-(2 :5-dichloro-4-sulfophenyl)-3-methyl-5" Yellbw.

' pyrazoone.

' 2 mols.-of 2*acetylaimino-E-naphtholJ-sulfonic acid' 'Orange-bro'ivn.

. 2 mols;of l-naphthoH-sulfonic acid; Scarlet. 2 mols. of.2-N-beta-hydroxyetfiylaminofi-naphthol-6 Brown.

sulfonic acid; 8 2 mols. 'of2 phenylamtdo S-naphthol-fi snlfonic acid j Brown 9 2 mols. of l-benzoylamino-8-naphth0l-4:6-disulfonic acid. Red. 10 2m01s. of 1-naphthol-4-sulfonic acid. Scarlet 11 2 mols. of2-phenylamino-S-naphthdl-fi-sulfonic acid Brown 12 2 mole. of 2phenylamino-8-1iaphthoI-6-su1fonic acid Brown V Example 3 41.8.parts of 3-:4' diamino-4-methylbenzoyl-N benzylanilide are dissolved in 'a-mixture of 625 parts of 36% aqueous hydrochloric acid and 600 parts of waterand tetrazotized at 0 --5 C. with a-solution of 17.2 parts of sodium-nitrite-in 125- pa-rts-of water. The tetrazo-solution is then added gradually to an ice=-cold solution which contains 63.6 parts of l-(-4 '-sulfophenyl)-3-methyl- S-pyrazoloneand 40 parts of anhydrous sodium carbonate in'800 partsof water. When coupling is complete the dye is salted out, filtered 011' and dried. The new dye has, in the form of free acid, the formula:

$0111 $0311 It is soluble in water and dyeswoolfromianacid 01- neutral bath in yellow" shads'ofvery good fastness to washing and milling. j The 3 :4' diamino-4-methylbenzoyl N-benzy1- anilide which is used above is a new compound, which is made as follows: A'solution of 6824 parts of 4'-nitro-N-'benzylaniline and 60 parts'of 3- nitr'o-4-methylbenzoyl chloridein 250 parts of toluene is boiled until the reaction iscomplete. The resulting 3 :4'-dinitro-4 methylbenzoyl N- ben'zylanilide (M. P. 154? C.) is'th'en reduced to the required diamine (M. P. 157 C.) with iron and hydrochloric acid in either water or ethyl alcohol.

4:3'-diaminobenzoyl-N-benzylanilide is a new compound and is made as follows: A solution containing 68.4 parts of 3-nitro-N-benzylaniline an-d55.8 parts of "p-nitrobenzoyl chloride in 450 parts of toluene is boiled until the reaction is 75 40 I claim-zis to be understood that I do not=limitmyse1f 35 to the specific embodimentsthereof except as defined in the appended claims. 7

This application isa division'of U. S. application Serial No. 219,097, filed Julyv 13,1938, U. S. Patent No. 2,216,229, issued October '1, 1940.

'1. The compounds represented by the "formula:

in which X and X are one of a group consisting of hydrogen and methyl and R and R are water soluble azo dyestuff coupling components from the class consisting of the arylpyrazolonesulfonic acid and alphanaphtholsulfonic acid series.

2. The compounds represented by the formula:

. I 5 CH2 CON in which X and X are one of a class consisting of hydrogen and methyl and R and R are Watersoluble azodyestufi coupling components of the aryl pyrazolonesulfonic acid series.

3. The compounds represented by the formula:

4. The compound represented by the formula:

6. The compound-represented by the formula:

V O I H: N=N l-N N=N SOaH WILFRID H. CLIFFE.

5. The compound represented by the formula: 

